CN104269461A - Film formation method of n-type In2S3 buffer layer and application of film formation method of n-type In2S3 buffer layer - Google Patents
Film formation method of n-type In2S3 buffer layer and application of film formation method of n-type In2S3 buffer layer Download PDFInfo
- Publication number
- CN104269461A CN104269461A CN201410500670.XA CN201410500670A CN104269461A CN 104269461 A CN104269461 A CN 104269461A CN 201410500670 A CN201410500670 A CN 201410500670A CN 104269461 A CN104269461 A CN 104269461A
- Authority
- CN
- China
- Prior art keywords
- film
- resilient coating
- substrate
- temperature
- horizontal pipe
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 58
- 230000015572 biosynthetic process Effects 0.000 title abstract 8
- 238000000137 annealing Methods 0.000 claims abstract description 22
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims description 50
- 239000011248 coating agent Substances 0.000 claims description 47
- 238000000576 coating method Methods 0.000 claims description 47
- 239000000843 powder Substances 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 28
- 229910052710 silicon Inorganic materials 0.000 claims description 21
- 239000010703 silicon Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 19
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- 239000010935 stainless steel Substances 0.000 claims description 11
- 239000004065 semiconductor Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 230000004888 barrier function Effects 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 241000931526 Acer campestre Species 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 7
- 239000004744 fabric Substances 0.000 claims description 7
- 230000003287 optical effect Effects 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- -1 polyethylene Polymers 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 4
- 238000012423 maintenance Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 3
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 2
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 238000009288 screen filtration Methods 0.000 claims description 2
- 239000010408 film Substances 0.000 abstract description 100
- 239000010409 thin film Substances 0.000 abstract description 21
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 2
- 239000013077 target material Substances 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 238000004549 pulsed laser deposition Methods 0.000 description 37
- 239000007789 gas Substances 0.000 description 24
- 239000000523 sample Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 10
- 238000000151 deposition Methods 0.000 description 9
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 238000000224 chemical solution deposition Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 2
- 229910052774 Proactinium Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- 101100008044 Caenorhabditis elegans cut-1 gene Proteins 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 238000003877 atomic layer epitaxy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0623—Sulfides, selenides or tellurides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/28—Vacuum evaporation by wave energy or particle radiation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electromagnetism (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention relates to a new film formation method of an n-type In2S3 buffer layer and application. According to the film formation method and the application, the shortcomings in the prior art for manufacturing the In2S3 buffer layer are overcome. The film formation method includes the steps of manufacturing an In2S3 cake, manufacturing an In2S3 target material block, manufacturing In2S3 thin film, conducting annealing, and obtaining the n-type indium sulfide buffer layer with the electrical resistivity smaller than or equal to 5*10<-3>Ohm cm. By means of a solar cell obtained by a product of the new film formation method, the open-circuit voltage is 0.29 V, and the short-circuit current is 7.7 nA. The new film formation method has the advantages that the film formation method and the product are good in thin film uniformity coincidence, good in conductivity, stable in chemical constitution, free of environmental pollution and the like.
Description
Technical field
The invention belongs to photovoltaic material preparing technical field, be specifically related to one and prepare N-shaped indium sulfide (n-In
2s
3) film build method of resilient coating, and by n-In
2s
3the solar cell that resilient coating obtains further.
Technical background
Energy crisis impels people more and more sight to be invested clean regenerative resource, as solar energy, wind energy etc.Solar energy is the most clean, the safe and reliable energy in future, starts from last century Mo, and making laws support one after another in countries in the world, makes photovoltaic generation industry become one of the fastest new industry of global evolution.
U.S.'s Bell Laboratory reported first monocrystaline silicon solar cell in 1954, open the New Times of p-n junction type solar cell, time up to now, p-n junction solar cell is still in occupation of the absolute status of photovoltaic art, and wherein inorganic compound is as cadmium telluride (CdTe), copper indium diselenide (CuInSe
2) etc. thin-film solar cells with its low cost, high conversion efficiency, be easy to the advantages such as large-scale production, cause people and pay close attention to greatly.
Cadmium sulfide (CdS) is current p-n junction solar cell application N-shaped padded coaming the most widely, for p-CdTe/n-CdS thin-film solar cells, it has the highest theoretical conversion efficiency (28%), the highest electricity conversion obtained in the lab has reached 17.3%, but the marketization is made slow progress, the market share only about 1%, wherein the use of toxic element Cd limits its application and the major reason promoted.Therefore people just actively find eco-friendly n-type semiconductor to replace the resilient coating of CdS as solar cell.
As the indium sulfide (In of III-VI compounds of group
2s
3) there are 3 kinds of different defect sturctures: α-In
2s
3(defect cube), β-In
2s
3(defect spinelle, with cube or the version in four directions exist) and γ-In
2s
3(defect stratiform six side), defect described herein, refers to that, in microstructure, molecular structure is had vacant position, and has nothing to do, wherein only have β-In with the crystallinity of material
2s
3can show the semiconductor conductive characteristic of N-shaped, energy gap is 2.00 ~ 2.30eV, in addition In
2s
3self not there is toxicity, stable performance, less and have excellent photoelectric properties to the absorption of visible light wave range, be applied to Cu (In, Ga) Se at present
2in thin-film solar cells, substitute CdS as resilient coating, obtain with the thin-film solar cells conversion efficiency closely of the CdS resilient coating of standard (R. Verma et al,
j. Appl. Phys.2010,108,074904), β-In is shown
2s
3be expected to replace the window material of CdS as thin-film solar cells.
Preparation In
2s
3the method of film usually have Co-evaporated Deposition method (J. George et al,
phys. stst. sol.1988, (a) 106,123), atomic layer epitaxy (M. Leskel et al,
appl. Surf. Sci.2006, (4) 122-125), electrodeposition process (B. Asenjo et al,
thin Solid Films2005,480 – 481,151-156) and chemical bath deposition method (patent of invention number: 200910088840.7) etc.Chemical bath deposition, electro-deposition liquid phase method equipment are simple, and process costs is lower, but has some limitations, as chemical bath deposition is longer for reaction time, be difficult to the film generating well-crystallized, electrodeposition process has requirement to substrate, can only at the Grown film of conduction.Vapor phase method carries out usually under high temperature, high vacuum condition, and production cost is relatively high, but is conducive to the In of well-crystallized
2s
3the generation of film, is thus still the main method of current thin film solar cell buffer layer deposition.But the more difficult accurate control thin film composition of existing gas phase deposition technology, this has an impact to the performance of film light transmission features and solar cell.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, the N-shaped In that conductivity is good, chemical composition is stable is provided
2s
3the film build method of resilient coating and application thereof.Its concrete film build method is as follows respectively with application:
N-shaped In
2s
3the film build method of resilient coating, carries out as follows:
Step 1: by In
2s
3target powder, after screen filtration, is placed in stainless steel mould and suppresses, and obtains In
2s
3cake block;
Step 2: by the In obtained by step 1
2s
3cake block is placed on to be calcined by the vacuum environment of Ar gas shielded; After completing calcining, together naturally cool to room temperature with horizontal pipe furnace; Obtain In
2s
3target block;
Step 3: by the In obtained by step 2
2s
3target block is installed on the working chamber target holder in PLD system, substrate is installed on the sample carrier of the working chamber of PLD system; 1 × 10
-4under the vacuum environment of below Pa, open the pulse laser of PLD system, and bombard aforesaid In
2s
3target block; Stimulated Light is bombarded and the molten In steamed
2s
3the particle of target is attached to the surface of substrate, grows and forms one deck In
2s
3film, described In
2s
3the resistivity of film is not less than 5 × 10
3Ω cm;
Step 4: have resistivity to be not less than 5 × 10 superficial growth obtained by step 3
3the In of Ω cm
2s
3quick anneal oven is put in the substrate of film, anneals in the vacuum environment of Ar gas shielded; Naturally cool, through the In that annealing in process obtains after completing annealing
2s
3it is 5 × 10 that the resistivity of film is not more than
-3Ω cm, and the conductive characteristic presenting significant n-type semiconductor, obtain the resilient coating being used for N-shaped indium sulfide.
Preferred scheme is, carries out as follows:
(1) 8g indium sulfide (In is got
2s
3) target powder carries out grinding and use 2000 object screen clothes to filter, by the In by screen cloth
2s
3it is in the stainless steel mould of 25mm that powder is placed on diameter, carries out continuous print three compactings: during first time compacting, jack applies the pressure of 10MPa and keeps 10 ~ 15min with jack; During second time compacting, jack applies the pressure of 20MPa and keeps 10 ~ 15min; During third time compacting, jack is pressurized to 40MPa and keeps 2 ~ 4h; When third time suppresses, every the actual applied pressure value that 30min checks a jack, if insufficient pressure 40MPa, then once pressurize, to keep the In in jack pair stainless steel mould
2s
3powder institute applied pressure is not less than 40MPa all the time; After completing third time compacting, namely obtain In
2s
3cake block; Described In
2s
3the diameter of cake block at 24.5mm to 26.0mm, thickness between 3.90mm to 4.10mm; Furtherly, described In
2s
3target powder is pure In
2s
3powder;
(2) In will obtained by step 1
2s
3cake block puts into horizontal pipe furnace, closes the valve of horizontal pipe furnace; The vacuum degree of horizontal pipe furnace is evacuated to below 0.1Pa by the vacuum pump first by being connected with horizontal pipe furnace one end; Opposite side subsequently to horizontal pipe furnace passes into the argon gas (Ar) the operation of continuation maintenance vacuum pump that flow is 10sccm to 50sccm, makes horizontal pipe furnace internal gas pressure maintain between 0.15MPa to 0.2MPa; The heater opening horizontal pipe furnace subsequently carries out two sections of intensifications: with the speed of 15 DEG C/min, the furnace temperature of horizontal pipe furnace is warmed up to 300 DEG C, and with the furnace temperature of 300 DEG C insulation 2h; Afterwards, with the speed of 15 DEG C/min, the furnace temperature of horizontal pipe furnace is warmed up to 700 DEG C by 300 DEG C, and with the furnace temperature of 300 DEG C insulation 4 ~ 5h; Finally, close the heater of horizontal pipe furnace, naturally cool to room temperature by horizontal pipe furnace; Obtain In
2s
3target block;
(3) In will obtained by step 2
2s
3target block is installed to pulsed laser deposition (Pulsed Laser Deposition, on the target holder of the PLD) working chamber of system, substrate is installed on the sample carrier of the working chamber of PLD system, close the valve of the working chamber of PLD system, and by the vacuum valve be connected with PLD system works chamber, the vacuum degree in working chamber is evacuated to 1 × 10
-4below Pa;
Subsequently, open the electric rotating machine of target holder and the electric rotating machine of sample carrier respectively, make target holder be rotated counterclockwise by the rotating speed of 5r/min, sample carrier turns clockwise by the rotating speed of 5r/min;
Afterwards, open the pulse laser of PLD system, the In described in the laser beam making pulse laser produce bombardment
2s
3target block, the molten In steamed by laser bombardment
2s
3the particle of target is attached to the surface of substrate, namely substrate superficial growth and form one deck In2S3 film; Wherein, the running parameter of pulse laser is: optical maser wavelength 248nm, pulse duration 25ns, and laser energy is 100mJ ~ 170mJ, and laser frequency is 3 ~ 5Hz, and the plated film time is 30min; Because substrate is without heating, the growth temperature of film is lower, and therefore crystal particle crystal boundary is comparatively remarkable, and the crystallinity of film is poor, and through adopting the electrical detection of Ji Shili company 4200 semiconductor parameter testing system, the resistivity of this film is not less than 5 × 10
3Ω cm, the film conductivity namely now obtained is poor;
Deposition preparation In is carried out at pulse laser
2s
3in the process of film, continuous firing answered by the vacuum valve be connected with PLD system works chamber, and the vacuum degree in the working chamber of PLD system is maintained 5 × 10
-3below Pa;
(4) quick anneal oven is put in the substrate of conductive for the superficial growth obtained by step 3 poor In2S3 film, with vacuum pump by after quick anneal oven forvacuum to 1Pa, in quick anneal oven, pass into Ar gas until the air pressure in quick anneal oven reaches atmospheric pressure; Repeat above-mentioned to short annealing stove evacuation and the step 2 time of filling Ar gas; Subsequently, continue in quick anneal oven, pass into Ar gas, and keep the air pressure of quick anneal oven between 0.02MPa ~ 0.04MPa, with the heating rate of 4 DEG C/s the furnace temperature of quick anneal oven risen to 300 DEG C and keep this temperature 30min; Afterwards, be naturally down to after normal temperature until quick anneal oven and take out, now, In
2s
3the resistivity of film is reduced to 5 × 10
-3below Ω cm, and the conductive characteristic presenting significant n-type semiconductor, prepare the N-shaped indium sulfide resilient coating for solar cell.It is β-In that XRD characterizes this film
2s
3.
Preferred scheme is, obtains the In in step 1 as follows
2s
3cake block: get 8g In
2s
3target powder carries out grinding and uses 2000 object screen clothes to filter, by the In by screen cloth
2s
3it is in the stainless steel mould of 25mm that powder is placed on diameter, put into press and carry out continuous print three intensification compactings: first, the pressure of press is set to 1450Psi(Pounds per square inch, pound per inch, 145Psi=1MPa), and by the heating rate of 3 ~ 6 DEG C/min by the heating temperatures of press working area to 60 DEG C, keep this pressure and temperature 5 ~ 15min subsequently; Subsequently, by the pressure adjusting of press to 2900Psi, and by the heating rate of 3 DEG C/min by the heating temperatures of press working area to 110 DEG C, keep this pressure and temperature 30 ~ 60 minutes subsequently; Afterwards, by the pressure adjusting of press to 5800psi, and the temperature of press working area is risen to 240 DEG C with the heating rate of 2 DEG C/min, and be incubated 90 minutes; Finally, the pressure of press is maintained 5800Psi, the temperature of press working area is progressively lowered the temperature with the rate of temperature fall being not more than 3 DEG C/min, until come out of the stove when the temperature of press working area is less than 40 DEG C, obtain In
2s
3cake block; Described In
2s
3the diameter of cake block at 24.5mm to 26.0mm, thickness between 3.60mm to 4.00mm; Intensification compacting can improve In better
2s
3the compactness of cake block, avoids in follow-up pulse-laser deposition technique, oarse-grained In
2s
3particulate is attached in substrate, affects uniformity and the electrical property of film forming.
Furtherly, described In
2s
3target powder is pure In
2s
3powder or In
2s
3form with the mixed-powder of S; Stating In
2s
3with the mixed-powder of S, the quality of S powder accounts for 0.2 ~ 1.0 ‰ of mixed-powder gross mass.The S powder of trace can improve the crystallization shape of end product.
Adopt N-shaped In of the present invention
2s
3the application of the product of resilient coating: by N-shaped In
2s
3resilient coating prepares solar cell, and this solar cell is by n-In
2s
3the resilient coating 3 of film and material are that the substrate 1 of p-Si forms, and material is the end face of the substrate 1 of p-Si and material is n-In
2s
3the bottom surface of the resilient coating 3 of film is connected; Be n-In in material
2s
3the end face of the resilient coating 3 of film be provided be arranged in array, thickness is 30 ~ 50nm and material is the round electrode 4 of metal In; In described material be the substrate 1 of p-Si bottom surface on be provided with the bottom electrode layer 2 that material is metal A g; Described n-In
2s
3the resistivity of the resilient coating 3 of film is 1.00 – 5.00 × 10
-3Ω cm; The open circuit voltage of described solar cell is 0.29 V, short circuit current is 7.7 nA.
Furtherly, β-In
2s
3the resistivity of the resilient coating 3 of film is 1.00-5.00 × 10
-3Ω cm, conductive characteristic is N-shaped.
beneficial effect of the present invention has:
1, the present invention adopts nontoxic In
2s
3in prepared by material
2s
3solar energy buffer layer thin film and be N-shaped, after annealing, conductive characteristic is good, is expected to the main flow cushioning layer material CdS replacing current high efficiency solar cell;
2, the present invention uses high-purity In first
2s
3target, by PLD method, realizes congruent same plated film, effectively can control the stoichiometric proportion of product film, thus stabilizing device performance;
3, this patent uses PLD to prepare In
2s
3film, deposition rate is high, and deposition cycle is short, low to substrate selectivity, and can obtain the film consistent with target material composition.This β-In prepared with the immersion method reported before
2s
3film is compared, and has advantage significantly, because immersion method prepares β-In
2s
3affect greatly by the ion concentration of reaction environment, pH value during film; And there is layering in sedimentation in it, In
2s
3density, the composition of film are stable, homogeneous not, cause this In
2s
3the electric conductivity of film is unstable, and then affects the performance of solar cell prepared therefrom, is not suitable for large batch of production.And, along with the carrying out of immersion method, during wherein the concentration of reactive ion also declines fast, cause the In as end product further
2s
3the composition of film and density are homogeneous not, at β-In
2s
3(the In of N-shaped conductive structure
2s
3) in mix and have a large amount of α-In
2s
3with γ-In
2s
3(nonconducting lattice structure), due to α-In
2s
3with γ-In
2s
3all do not manifest the semiconductor conductive characteristic of N-shaped, can cause there is a large amount of microcosmic, nonconducting region in the solar energy film prepared by the method, can there is exception in aforementioned areas in electric charge, and then affect performance and the power consumption of monoblock solar cell;
4, this patent uses In prepared by PLD
2s
3the existence before and after annealing of Thin film conductive characteristic changes significantly, and resistivity is by 5 × 10
3Ω cm drops to 5 × 10
-3below Ω cm, and by measuring, prepared In
2s
3thin film conductive type is N-shaped;
5, by the solar cell resilient coating that a process for preparing (n-In namely after annealed process
2s
3film) resistivity be not more than 5 × 10
-3Ω cm, the mean roughness of film surface is not more than 0.575nm, and average particulate diameter is less than 94.6nm, excellent performance.It is pointed out that this method obtains the crystal structure of uniformity is β-In
2s
3n-In
2s
3(N-shaped In
2s
3) be that two steps complete: first prepare even density, In that thickness is consistent
2s
3film, more annealed by In
2s
3being converted into crystal structure is β-In
2s
3n-In
2s
3, avoiding in the finished product of preparation to mix has α-In
2s
3or γ-In
2s
3and the hydraulic performance decline caused, fault of construction;
6, the open circuit voltage adopting the solar cell of the solar cell resilient coating of this method is 0.29 V, and short circuit current is 7.7 nA, and fill factor, curve factor is 0.39, shows the β-In prepared by the method
2s
3effectively can be applied to the resilient coating of thin-film solar cells, performance and other technique existing (such as immersion method) keep suitable while, reduce the production difficulty of product, and improve the consistency of production efficiency and film forming.
Accompanying drawing explanation
Fig. 1 is the In that embodiment 1 is prepared by PLD
2s
3the uv-visible absorption spectra figure of solar energy buffer layer thin film.
Fig. 2 is the In that embodiment 1 is prepared by PLD
2s
3j-V characteristic curve before the annealing of solar energy buffer layer thin film.
Fig. 3 is the In that embodiment 1 is prepared by PLD
2s
3j-V characteristic curve after the annealing of solar energy buffer layer thin film.
Fig. 4 is the In that embodiment 2 is prepared by PLD
2s
3the XRD collection of illustrative plates of solar energy buffer layer thin film.
Fig. 5 is the In that embodiment 2 is prepared by PLD
2s
3the AFM photo of solar energy buffer layer thin film.
Fig. 6 is the In that embodiment 2 is prepared by PLD
2s
3the EDS collection of illustrative plates of solar energy buffer layer thin film.
Fig. 7 is n-In in embodiment 2
2s
3the silicon heterogenous solar battery structure schematic top plan view of film/p-.
Fig. 8 is n-In in embodiment 2
2s
3the silicon heterogenous solar battery structure schematic side view of film/p-.
Fig. 9 is n-In prepared in embodiment 2
2s
3the silicon heterogenous solar cell of film/p-is 350 μ w/cm in unglazed and intensity of illumination
2white light under electric current and voltage characteristic.
Figure 10 is the In that embodiment 3 is prepared by PLD
2s
3j-V characteristic curve under the different grid voltage of solar energy buffer layer thin film.
Sequence number in figure is: 1 is p-silicon base, and 2 is Ag electrode layer, and 3 is N-shaped In
2s
3film, 4 is circular hole In electrode.
Embodiment
Now be described with reference to the accompanying drawings design feature of the present invention.
Prepare N-shaped In
2s
3the method of resilient coating, carry out as follows:
(1) 8g In is got
2s
3target powder carries out grinding and uses 2000 object screen clothes to filter, by the In by screen cloth
2s
3it is in the stainless steel mould of 25mm that powder is placed on diameter, carries out continuous print three compactings: during first time compacting, jack applies the pressure of 10MPa and keeps 10min with jack; During second time compacting, jack applies the pressure of 20MPa and keeps 10min; During third time compacting, jack is pressurized to 40MPa and keeps 2h; When third time suppresses, every the actual applied pressure value that 30min checks a jack, if insufficient pressure 40MPa, then once pressurize, to keep the In in jack pair stainless steel mould
2s
3powder institute applied pressure is not less than 40MPa all the time; After completing third time compacting, namely obtain In
2s
3cake block; Described In
2s
3the diameter of cake block is about 26.0mm, thickness is about 4.10mm;
(2) In will obtained by step 1
2s
3cake block puts into horizontal pipe furnace, closes the valve of horizontal pipe furnace; The vacuum degree of horizontal pipe furnace is evacuated to below 0.1Pa by the vacuum pump first by being connected with horizontal pipe furnace one end; Opposite side subsequently to horizontal pipe furnace passes into the argon gas (Ar) the operation of continuation maintenance vacuum pump that flow is 10sccm, makes horizontal pipe furnace internal gas pressure maintain 0.15MPa; The heater opening horizontal pipe furnace subsequently carries out two sections of intensifications: with the speed of 15 DEG C/min, the furnace temperature of horizontal pipe furnace is warmed up to 300 DEG C, and with the furnace temperature of 300 DEG C insulation 2h; Afterwards, with the speed of 15 DEG C/min, the furnace temperature of horizontal pipe furnace is warmed up to 700 DEG C by 300 DEG C, and with the furnace temperature of 300 DEG C insulation 4h; Finally, close the heater of horizontal pipe furnace, naturally cool to room temperature by horizontal pipe furnace; Obtain In
2s
3target block;
(3) In will obtained by step 2
2s
3target block is installed on the target holder of the working chamber of PLD system, substrate is installed on the sample carrier of the working chamber of PLD system, close the valve of the working chamber of PLD system, and by the vacuum valve be connected with PLD system works chamber, the vacuum degree in working chamber is evacuated to 1 × 10
-4below Pa;
Subsequently, open the electric rotating machine of target holder and the electric rotating machine of sample carrier respectively, make target holder be rotated counterclockwise by the rotating speed of 5r/min, sample carrier turns clockwise by the rotating speed of 5r/min;
Afterwards, open the pulse laser of PLD system, the In described in the laser beam making pulse laser produce bombardment
2s
3target block, the In sputtered by laser bombardment
2s
3the particle of target is attached to the surface of substrate, grows and forms one deck In
2s
3film, the resistivity of this film is not less than 5 × 10
3Ω cm, the film conductivity namely now obtained is poor; Wherein, the running parameter of pulse laser is: optical maser wavelength 248nm, pulse duration 25ns, and laser energy is 100mJ ~ 170mJ, and laser frequency is 3 ~ 5Hz, and the plated film time is 30min;
Carry out at pulse laser depositing in the process of preparation In2S3 film, continuous firing answered by the vacuum valve be connected with PLD system works chamber, and the vacuum degree in the working chamber of PLD system is maintained 5 × 10
-3below Pa;
(4) poor (resistivity is greater than 5 × 10 by conductive for the superficial growth that obtained by step 3
3Ω cm) the substrate of n-In2S3 film put into quick anneal oven, with vacuum pump by after quick anneal oven forvacuum to 1Pa, in quick anneal oven, pass into Ar gas until the air pressure in quick anneal oven reaches atmospheric pressure; Repeat above-mentioned to short annealing stove evacuation and the step 2 time of filling Ar gas; Subsequently, continue in quick anneal oven, pass into Ar gas, and keep the air pressure of quick anneal oven between 0.02MPa ~ 0.04MPa, with the heating rate of 4 DEG C/s the furnace temperature of quick anneal oven risen to 300 DEG C and keep this temperature 30min, naturally be down to after normal temperature until quick anneal oven afterwards and take out, final acquisition surface is the substrate of N-shaped indium sulfide resilient coating, the In after annealed process
2s
3the resistivity of film is not more than 5 × 10
-3Ω cm, the 4200 type characteristic of semiconductor analytical systems that N-shaped conductive characteristic is produced by Keithley (Keithley) instrument company and AC15A type DC detecting meter verified; In addition, by HRTEM(high-resolution lens), SEM(scanning electron microscopy) and AFM(atomic force microscope) detection with mutually verify, the mean roughness of the film surface adopting this method to prepare is not more than 0.575nm, and average particulate diameter is less than 94.6nm.In step 3, be β-In by PLD plated film product
2s
3, annealing improves β-In
2s
3the crystallinity of crystal grain, causes conductance to significantly improve, thus makes composition be β-In
2s
3indium sulfide thin film finally present N-shaped characteristic.
Furtherly, described substrate is glass, resistivity is less than 5.1 × 10
-3the P-type silicon sheet of Ω cm, with the silicon chip of insulating barrier or flexible insulating substrate.
Furtherly, described insulating barrier is SiO
2, Si
3n
4or HfO
2in one, and the resistivity of insulating barrier is greater than 1 × 10
3Ω cm, the thickness of insulating barrier is 100 ~ 500nm; Described flexible insulating substrate is PETG, polyethylene, polypropylene, polystyrene, polyethylene naphthalate or polyether sulfone, and the resistivity of flexible insulating substrate is greater than 1 × 10
4Ω cm.
Furtherly, In
2s
3target powder is pure In
2s
3powder is formed, described In
2s
3the purity of powder is not less than 99.98%.
Adopt and of the present inventionly prepare N-shaped In
2s
3the solar cell that the product that the method for resilient coating obtains is prepared further, this solar cell is by n-In
2s
3the resilient coating 3 of film and material are that the substrate 1 of p-Si forms; Described n-In
2s
3the resilient coating 3 of film is β-In
2s
3film is formed.Material is the end face of the substrate 1 of p-Si and material is n-In
2s
3the bottom surface of the resilient coating 3 of film is connected; Be n-In in material
2s
3the end face of the resilient coating 3 of film be provided be arranged in array, thickness is 30 ~ 50nm and material is the round electrode 4 of metal In; In described material be the substrate 1 of p-Si bottom surface on be provided with the bottom electrode layer 2 that material is metal A g; Described n-In
2s
3the resistivity of the resilient coating 3 of film is 1.00 – 5.00 × 10
-3Ω cm; The open circuit voltage of described solar cell is 0.29 V, short circuit current is 7.7 nA, and fill factor, curve factor is 0.39.
Furtherly, described material is that the conductivity of the substrate 1 of p-Si is greater than 5.1 × 10
-3Ω cm.
Furtherly, the β-In of spinel structure
2s
3the resistivity of the resilient coating 3 of film is 1.00-5.00 × 10
-3Ω cm, conductive characteristic is N-shaped.
Furtherly, the β-In of spinel structure
2s
3the mean roughness of the film surface of the resilient coating 3 of film is not more than 0.575nm, and average particulate diameter is less than 94.6nm.
Below in conjunction with embodiment to further instruction of the present invention.
Embodiment 1
Employing glass is substrate, is immersed in difference ultrasonic cleaning 8min in acetone, ethanol, deionized water successively, is placed in vacuum drying chamber and dries after taking-up; In
2s
3compound target is fixed on target holder, and silicon chip is fixed on sample carrier, and vacuum chamber temperature is normal temperature, and vacuum is evacuated to 5 × 10
-3below Pa, target holder rotating speed is counterclockwise 5r/min, and sample carrier rotating speed is clockwise 5r/min, optical maser wavelength 248nm, pulse duration 25ns, and laser energy is 154mJ, and laser frequency is 5Hz, and the plated film time is 30min.By after quick anneal oven forvacuum to 1Pa during annealing, pass into Ar gas to atmospheric pressure, then vacuumize, repeatedly vacuumize, inflate 2 times, constantly pass into Ar gas subsequently, keep air pressure about 0.04MPa, be warming up to 300 DEG C with the speed of 4 DEG C/s, keep this temperature 30min, be down to normal temperature afterwards.Fig. 1 is uv-visible absorption spectra, and matching can obtain, and film energy gap is about 2.2eV.
Fig. 2 is the J-V figure of film before annealing, and from figure, when 1V, current density is only 0.08 nA/cm
2, the conductivity of visible film is poor.Fig. 3 is the J-V figure of annealing rear film, and from figure, when 1V, current density is 95 μ A/ cm
2, conductivity significantly improves.
Embodiment 2
Adopt p-type silicon chip to be substrate 1, be immersed in difference ultrasonic cleaning 8min in acetone, ethanol, deionized water successively, be placed on after taking-up in vacuum drying chamber and dry; In
2s
3compound target is fixed on target holder, and silicon chip is fixed on sample carrier, and vacuum chamber temperature is normal temperature, and vacuum is evacuated to 5 × 10
-3below Pa, target holder rotating speed is counterclockwise 5r/min, and sample carrier rotating speed is clockwise 5r/min, optical maser wavelength 248nm, pulse duration 25ns, and laser energy is 174mJ, and laser frequency is 5Hz, and the plated film time is 30min.By after quick anneal oven forvacuum to below 1Pa during annealing, pass into Ar gas to atmospheric pressure, repeat to vacuumize, inflate 2 times, pass into Ar gas subsequently and keep air pressure about 0.04MPa, be warming up to 300 DEG C with the speed of 4 DEG C/s, keep this temperature 30min, be down to normal temperature afterwards.Fig. 4 is the XRD collection of illustrative plates of film, through contrast, its diffraction maximum and JCPDS card 32-0456 basically identical, therefore we think that product film is cubic system β-In
2s
3.Fig. 5 is the AFM photo of film, film surface mean roughness 0.575nm, average particulate diameter 94.6nm, and surface uniform, without obvious particle.Fig. 6 is EDS collection of illustrative plates, and visible product In2S3 film is only containing In, S two kinds of elements, and stoichiometric proportion is 2:3, and confirmation product is In
2s
3, wherein Si is from substrate.
For test I n
2s
3the photovoltaic property of film, we construct n-In as shown in Figure 7,8
2s
3the silicon heterogenous solar cell of film/p-.Use diameter is the circular hole mask plate of 1.5 mm, adopts the method for thermal evaporation, is less than 10 at air pressure
-3under the condition of Pa, at n-In
2s
3it is 30 ~ 50nm metal In electrode layer 4 that thickness is prepared on the surface of thin layer 3; The method of smearing is adopted to prepare metal A g electrode layer 2 at the lower surface of described p-silicon substrate layer 1.Fig. 9 is n-In prepared in the present invention
2s
3the silicon heterogenous solar cell of film/p-is 350 μ W/cm in unglazed and intensity of illumination
2white light under electric current and voltage characteristic, the n-In prepared as seen from the figure
2s
3film/p-is silicon heterogenous has obvious photovoltaic property, and wherein open circuit voltage is 0.29 V, and short circuit current is 7.7 nA, and fill factor, curve factor is 0.39.
Embodiment 3
Adopt oxidized silicon chip as substrate, be immersed in difference ultrasonic cleaning 8min in acetone, ethanol, deionized water successively, be placed on after taking-up in vacuum drying chamber and dry; In
2s
3compound target is fixed on target holder, and silicon chip is fixed on sample carrier, and vacuum chamber temperature is normal temperature, and vacuum is evacuated to 5 × 10
-3below Pa, target holder rotating speed is counterclockwise 5r/min, and sample carrier rotating speed is clockwise 5r/min, optical maser wavelength 248nm, pulse duration 25ns, and laser energy is 114mJ, and laser frequency is 5Hz, and the plated film time is 30min.By after quick anneal oven forvacuum to below 1Pa during annealing, pass into Ar gas to atmospheric pressure, then vacuumize, repeatedly vacuumize, inflate 2 times, constantly pass into Ar gas subsequently, keep air pressure about 0.04MPa, be warming up to 300 DEG C with the speed of 4 DEG C/s, keep this temperature 30min, be down to normal temperature afterwards.Adopt the method for thermal evaporation, be less than 10 at air pressure
-3under the condition of Pa, at n-type In
2s
3a pair 30 ~ 50nm metal In electrodes are prepared on the surface of thin layer, silicon base with silicon dioxide insulating layer is cut 1 little bar from edge, expose fresh section, silicon layer is connected again with scale copper, fixing in case anti-avulsion falls with silver slurry, thus an indium electrode adds source-drain voltage, an indium electrode grounding, silicon adds grid voltage, bottom gate type field-effect transistor (FET) can be formed.Figure 10 be grid voltage scope from-60V to 60V, when step-length is 40V, the J-V curve of film, as seen from the figure along with the increase of grid voltage, the corresponding increase of conductance of In2S3 film is typical N-shaped conductance, another consistent with AC15A type DC detecting meter (cold-hot probe) measured result.
Embodiment 4
(1) 8g In is got
2s
3target powder carries out grinding and filtering, by the In by screen cloth
2s
3powder is placed in stainless steel mould, continuous print three intensification compactings are carried out: first by press, the pressure of press is set to 1450Psi(10MPa), and by the heating rate of 6 DEG C/min by the heating temperatures of press working area to 60 DEG C, keep this pressure and temperature 15min subsequently; Subsequently, by the pressure adjusting of press to 2900Psi(20MPa), and by the heating rate of 3 DEG C/min by the heating temperatures of press working area to 110 DEG C, keep this pressure and temperature 30 minutes subsequently; Afterwards, by the pressure adjusting of press to 5800psi(40MPa), and the temperature of press working area is risen to 240 DEG C with the heating rate of 2 DEG C/min, and be incubated 90 minutes; Finally, the pressure of press is maintained 5800Psi(40MPa), the temperature of press working area is progressively lowered the temperature with the rate of temperature fall of 2 DEG C/min, until come out of the stove when the temperature of press working area is less than 40 DEG C, obtains In
2s
3cake block; Described In
2s
3the diameter of cake block is about 24.8mm, thickness is about 3.62mm; In in the present embodiment
2s
3target powder is In
2s
3with the mixed-powder of S, wherein the quality of S powder accounts for 0.2 ‰ of gross mass;
(2) In will obtained by step 1
2s
3cake block puts into horizontal pipe furnace, closes the valve of horizontal pipe furnace; The vacuum degree of horizontal pipe furnace is evacuated to below 0.1Pa by the vacuum pump first by being connected with horizontal pipe furnace one end; Opposite side subsequently to horizontal pipe furnace passes into the Ar gas the operation of continuation maintenance vacuum pump that flow is 50sccm, makes horizontal pipe furnace internal gas pressure maintain between 0.2MPa; The heater opening horizontal pipe furnace subsequently carries out two sections of intensifications: with the speed of 15 DEG C/min, the furnace temperature of horizontal pipe furnace is warmed up to 300 DEG C, and with the furnace temperature of 300 DEG C insulation 2h; Afterwards, with the speed of 15 DEG C/min, the furnace temperature of horizontal pipe furnace is warmed up to 700 DEG C by 300 DEG C, and with the furnace temperature of 300 DEG C insulation 5h; Finally, close the heater of horizontal pipe furnace, naturally cool to room temperature by horizontal pipe furnace; Obtain In
2s
3target block;
(3) In will obtained by step 2
2s
3target block is installed on the target holder of the working chamber of PLD system, substrate is installed on the sample carrier of the working chamber of PLD system, close the valve of the working chamber of PLD system, and by the vacuum valve be connected with PLD system works chamber, the vacuum degree in working chamber is evacuated to 1 × 10
-4below Pa;
Subsequently, open the electric rotating machine of target holder and the electric rotating machine of sample carrier respectively, make target holder be rotated counterclockwise by the rotating speed of 5r/min, sample carrier turns clockwise by the rotating speed of 5r/min;
Afterwards, open the pulse laser of PLD system, the In described in the laser beam making pulse laser produce bombardment
2s
3target block, the molten In steamed by laser bombardment
2s
3the particle of target is attached to the surface of substrate, grows and forms one deck In
2s
3film, described In
2s
3the resistivity of film is not less than 5 × 10
3Ω cm, namely now gained film conductivity is poor; Wherein, the running parameter of pulse laser is: optical maser wavelength 248nm, pulse duration 25ns, and laser energy is 100mJ ~ 170mJ, and laser frequency is 3 ~ 5Hz, and the plated film time is 30min;
Deposition preparation In is carried out at pulse laser
2s
3in the process of film, continuous firing answered by the vacuum valve be connected with PLD system works chamber, and the vacuum degree in the working chamber of PLD system is maintained 5 × 10
-3below Pa;
(4) resistivity there is is to be not less than 5 × 10 the superficial growth obtained by step 3
3the In of Ω cm
2s
3quick anneal oven is put in the substrate of film, with vacuum pump by after quick anneal oven forvacuum to below 1Pa, passes into Ar gas until the air pressure in quick anneal oven reaches atmospheric pressure in quick anneal oven; Repeat above-mentioned to short annealing stove evacuation and the step 2 time of filling Ar gas; Subsequently, continue in quick anneal oven, pass into Ar gas, and keep the air pressure of quick anneal oven between 0.04MPa, with the heating rate of 4 DEG C/s the furnace temperature of quick anneal oven risen to 300 DEG C and keep this temperature 30min; Afterwards, be naturally down to after normal temperature until quick anneal oven and take out, obtaining surperficial matter is N-shaped In
2s
3the substrate of resilient coating; Through the In that annealing in process obtains
2s
3the resistivity of film is 0.20 ~ 3.00 × 10
-3Ω cm, and the conductive characteristic presenting significant n-type semiconductor, obtain the resilient coating of the N-shaped indium sulfide being used for solar cell.
In the present embodiment, because the content of S powder is extremely low, therefore can not directly detect its composition by instruments such as SEM, HRTEM.But by pattern and the performance of product obtained by the method, the technique effect of energy indirect verification this method.Through the In that annealing in process obtains
2s
3the resistivity of film is on average 0.20 ~ 0.60 × 10
-3Ω cm, the mean roughness mean value of film surface is about 0.255nm, and average particulate diameter is at 67.5 ~ 74.6nm.
Claims (8)
1.n type In
2s
3the film build method of resilient coating, is characterized in that: carry out as follows:
Step 1: by In
2s
3target powder, after screen filtration, is placed in stainless steel mould and suppresses, and obtains In
2s
3cake block;
Step 2: by the In obtained by step 1
2s
3cake block is placed on to be calcined by the vacuum environment of Ar gas shielded; After completing calcining, together naturally cool to room temperature with horizontal pipe furnace; Obtain In
2s
3target block;
Step 3: by the In obtained by step 2
2s
3target block is installed on the working chamber target holder in PLD system, substrate is installed on the sample carrier of the working chamber of PLD system; 1 × 10
-4under the vacuum environment of below Pa, open the pulse laser of PLD system, and bombard aforesaid In
2s
3target block; Stimulated Light is bombarded and the molten In steamed
2s
3the particle of target is attached to the surface of substrate, grows and forms one deck In
2s
3film, described In
2s
3the resistivity of film is not less than 5 × 10
3Ω cm;
Step 4: have resistivity to be not less than 5 × 10 superficial growth obtained by step 3
3the In of Ω cm
2s
3quick anneal oven is put in the substrate of film, anneals in the vacuum environment of Ar gas shielded; Naturally cool, through the In that annealing in process obtains after completing annealing
2s
3it is 5 × 10 that the resistivity of film is not more than
-3Ω cm, and the conductive characteristic presenting significant n-type semiconductor, namely obtain N-shaped In
2s
3resilient coating.
2. N-shaped In as claimed in claim 1
2s
3the film build method of resilient coating, is characterized in that: carry out as follows:
(1) 8g In is got
2s
3target powder carries out grinding and uses 2000 object screen clothes to filter, by the In by screen cloth
2s
3it is in the stainless steel mould of 25mm that powder is placed on diameter, carries out continuous print three compactings: during first time compacting, jack applies the pressure of 10MPa and keeps 10 ~ 15min with jack; During second time compacting, jack applies the pressure of 20MPa and keeps 10 ~ 15min; During third time compacting, jack is pressurized to 40MPa and keeps 2 ~ 4h; When third time suppresses, every the actual applied pressure value that 30min checks a jack, if insufficient pressure 40MPa, then once pressurize, to keep the In in jack pair stainless steel mould
2s
3powder institute applied pressure is not less than 40MPa all the time; After completing third time compacting, namely obtain In
2s
3cake block; Described In
2s
3the diameter of cake block at 24.5mm to 26.0mm, thickness between 3.90mm to 4.10mm;
(2) In will obtained by step 1
2s
3cake block puts into horizontal pipe furnace, closes the valve of horizontal pipe furnace; The vacuum degree of horizontal pipe furnace is evacuated to below 0.1Pa by the vacuum pump first by being connected with horizontal pipe furnace one end; Opposite side subsequently to horizontal pipe furnace passes into the Ar gas the operation of continuation maintenance vacuum pump that flow is 10sccm to 50sccm, makes horizontal pipe furnace internal gas pressure maintain between 0.15MPa to 0.2MPa; The heater opening horizontal pipe furnace subsequently carries out two sections of intensifications: with the speed of 15 DEG C/min, the furnace temperature of horizontal pipe furnace is warmed up to 300 DEG C, and with the furnace temperature of 300 DEG C insulation 2h; Afterwards, with the speed of 15 DEG C/min, the furnace temperature of horizontal pipe furnace is warmed up to 700 DEG C by 300 DEG C, and with the furnace temperature of 300 DEG C insulation 4 ~ 5h; Finally, close the heater of horizontal pipe furnace, naturally cool to room temperature by horizontal pipe furnace; Obtain In
2s
3target block;
(3) In will obtained by step 2
2s
3target block is installed on the target holder of the working chamber of PLD system, substrate is installed on the sample carrier of the working chamber of PLD system, close the valve of the working chamber of PLD system, and by the vacuum valve be connected with PLD system works chamber, the vacuum degree in working chamber is evacuated to 1 × 10
-4below Pa;
Subsequently, open the electric rotating machine of target holder and the electric rotating machine of sample carrier respectively, make target holder be rotated counterclockwise by the rotating speed of 5r/min, sample carrier turns clockwise by the rotating speed of 5r/min;
Afterwards, open the pulse laser of PLD system, the In described in the laser beam making pulse laser produce bombardment
2s
3target block, the molten In steamed by laser bombardment
2s
3the particle of target is attached to the surface of substrate, grows and forms one deck In
2s
3film, described In
2s
3the resistivity of film is not less than 5 × 10
3Ω cm, namely now gained film conductivity is poor; Wherein, the running parameter of pulse laser is: optical maser wavelength 248nm, pulse duration 25ns, and laser energy is 100mJ ~ 170mJ, and laser frequency is 3 ~ 5Hz, and the plated film time is 30min;
Deposition preparation In is carried out at pulse laser
2s
3in the process of film, continuous firing answered by the vacuum valve be connected with PLD system works chamber, and the vacuum degree in the working chamber of PLD system is maintained 5 × 10
-3below Pa;
(4) resistivity there is is to be not less than 5 × 10 the superficial growth obtained by step 3
3the In of Ω cm
2s
3quick anneal oven is put in the substrate of film, with vacuum pump by after quick anneal oven forvacuum to below 1Pa, passes into Ar gas until the air pressure in quick anneal oven reaches atmospheric pressure in quick anneal oven; Repeat above-mentioned to short annealing stove evacuation and the step 2 time of filling Ar gas; Subsequently, continue in quick anneal oven, pass into Ar gas, and keep the air pressure of quick anneal oven between 0.02MPa ~ 0.04MPa, with the heating rate of 4 DEG C/s the furnace temperature of quick anneal oven risen to 300 DEG C and keep this temperature 30min; Afterwards, be naturally down to after normal temperature until quick anneal oven and take out, obtaining surperficial matter is N-shaped In
2s
3the substrate of resilient coating; Through the In that annealing in process obtains
2s
3it is 5 × 10 that the resistivity of film is not more than
-3Ω cm, and the conductive characteristic presenting significant n-type semiconductor, obtain the resilient coating of N-shaped indium sulfide.
3. prepare N-shaped In as claimed in claim 1
2s
3the method of resilient coating, is characterized in that, described In
2s
3target powder is separately by In
2s
3powder is formed.
4. N-shaped In as claimed in claim 1
2s
3the film build method of resilient coating, is characterized in that: obtain In by step 1
2s
3the concrete steps of cake block are as follows:
Get In
2s
3target powder carries out grinding and filtering with screen cloth, by the In by screen cloth
2s
3powder puts into stainless steel mould, carries out continuous print three intensification compactings by press:
First, the pressure of press is set to 10MPa, and by the heating rate of 3 ~ 6 DEG C/min by the heating temperatures of press working area to 60 DEG C, keep this pressure and temperature 5 ~ 15min subsequently;
Subsequently, by the pressure adjusting of press to 20MPa, and by the heating rate of 3 DEG C/min by the heating temperatures of press working area to 110 DEG C, keep this pressure and temperature 30 ~ 60 minutes subsequently;
Afterwards, by the pressure adjusting of press to 40MPa, and the temperature of press working area is risen to 240 DEG C with the heating rate of 2 DEG C/min, and be incubated 90 minutes;
Finally, the pressure of press is maintained 40MPa, the temperature of press working area is progressively lowered the temperature with the rate of temperature fall being not more than 3 DEG C/min, until come out of the stove when the temperature of press working area is less than 40 DEG C, obtain In
2s
3cake block.
5. N-shaped In as claimed in claim 2
2s
3the film build method of resilient coating, is characterized in that: described substrate be glass, silicon chip, with the silicon chip of insulating barrier or flexible insulating substrate.
6. any N-shaped In as described in claim 1 to 5
2s
3the film build method of resilient coating, is characterized in that: described insulating barrier is SiO
2, Si
3n
4or HfO
2in one, and the resistivity of insulating barrier is greater than 1 × 10
3Ω cm, the thickness of insulating barrier is 100 ~ 500nm; Described flexible insulating substrate is PETG, polyethylene, polypropylene, polystyrene, polyethylene naphthalate or polyether sulfone, and the resistivity of flexible insulating substrate is greater than 1 × 10
4Ω cm.
7. adopt any N-shaped In as described in claim 1 to 6
2s
3the application of the product that the film build method of resilient coating obtains, is characterized in that: by this N-shaped In
2s
3resilient coating prepares solar cell; This solar cell comprises n-In
2s
3the resilient coating (3) of film and material are the substrate (1) of p-Si, and material is the end face of the substrate (1) of p-Si and material is n-In
2s
3the bottom surface of the resilient coating (3) of film is connected; Be n-In in material
2s
3the end face of the resilient coating (3) of film be provided be arranged in array, thickness is 30 ~ 50nm and material is the round electrode (4) of metal In; In described material be the substrate (1) of p-Si bottom surface on be provided with the bottom electrode layer (2) that material is metal A g; Described n-In
2s
3the resistivity of the resilient coating (3) of film is 1.00 – 5.00 × 10
-3Ω cm; The open circuit voltage of described solar cell is 0.29 V, short circuit current is 7.7 nA.
8. solar cell as claimed in claim 7, it is characterized in that, described material is that the resistivity of the substrate (1) of p-Si is less than 5.1 × 10
-3Ω cm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410500670.XA CN104269461B (en) | 2014-09-26 | 2014-09-26 | N-shaped In2s3the film build method of cushion and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410500670.XA CN104269461B (en) | 2014-09-26 | 2014-09-26 | N-shaped In2s3the film build method of cushion and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104269461A true CN104269461A (en) | 2015-01-07 |
| CN104269461B CN104269461B (en) | 2016-07-06 |
Family
ID=52160968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410500670.XA Active CN104269461B (en) | 2014-09-26 | 2014-09-26 | N-shaped In2s3the film build method of cushion and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104269461B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105655423A (en) * | 2016-01-19 | 2016-06-08 | 合肥工业大学 | Nano heterojunction solar cell based on chalcogenide cuprous compound and preparation method thereof |
| CN109811362A (en) * | 2019-03-20 | 2019-05-28 | 齐鲁工业大学 | A method of utilizing indium sulfide/nickel cobalt aluminium houghite composite membrane photoelectrocatalysioxidization oxidization xylose |
| CN113213938A (en) * | 2021-05-20 | 2021-08-06 | 先导薄膜材料有限公司 | Preparation method of fine indium sulfide powder and target material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643032A (en) * | 2011-02-22 | 2012-08-22 | 浙江大学 | Method for preparing In2S3 film by chemical bath deposition |
| CN103074583A (en) * | 2013-01-25 | 2013-05-01 | 合肥工业大学 | Laser deposition preparation technology of CIGS film cell |
| CN103233202A (en) * | 2013-02-19 | 2013-08-07 | 广州金升阳科技有限公司 | Method for preparing CuInS2 nanorods by pulsed laser deposition |
-
2014
- 2014-09-26 CN CN201410500670.XA patent/CN104269461B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643032A (en) * | 2011-02-22 | 2012-08-22 | 浙江大学 | Method for preparing In2S3 film by chemical bath deposition |
| CN103074583A (en) * | 2013-01-25 | 2013-05-01 | 合肥工业大学 | Laser deposition preparation technology of CIGS film cell |
| CN103233202A (en) * | 2013-02-19 | 2013-08-07 | 广州金升阳科技有限公司 | Method for preparing CuInS2 nanorods by pulsed laser deposition |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105655423A (en) * | 2016-01-19 | 2016-06-08 | 合肥工业大学 | Nano heterojunction solar cell based on chalcogenide cuprous compound and preparation method thereof |
| CN105655423B (en) * | 2016-01-19 | 2017-04-05 | 合肥工业大学 | A kind of nano heterogeneous joint solar cell based on chalcogen cuprous compound and preparation method thereof |
| CN109811362A (en) * | 2019-03-20 | 2019-05-28 | 齐鲁工业大学 | A method of utilizing indium sulfide/nickel cobalt aluminium houghite composite membrane photoelectrocatalysioxidization oxidization xylose |
| CN113213938A (en) * | 2021-05-20 | 2021-08-06 | 先导薄膜材料有限公司 | Preparation method of fine indium sulfide powder and target material |
| CN113213938B (en) * | 2021-05-20 | 2022-12-20 | 先导薄膜材料有限公司 | Preparation method of fine indium sulfide powder and target material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104269461B (en) | 2016-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhao et al. | Single crystalline CH3NH3PbI3 self-grown on FTO/TiO2 substrate for high efficiency perovskite solar cells | |
| CN101692357B (en) | Method for preparing pile face doped zinc oxide transparent conductive film | |
| Salman et al. | Effective conversion efficiency enhancement of solar cell using ZnO/PS antireflection coating layers | |
| CN102651428B (en) | Fabrication method of gradient ferroelectric film solar cell | |
| CN104134720A (en) | Preparation method of organic and inorganic hybridization perovskite material growing by single-source flash evaporation method and plane solar cell of material | |
| KR101170681B1 (en) | Method for fabricating a CIGS thin film | |
| US20140057416A1 (en) | Semiconductive micro- and nano-wire array manufacturing | |
| CN104916785A (en) | CH3NH3PbI3 thin-film solar cell preparation method | |
| Yang et al. | Electrodeposited p-type Cu2O thin films at high pH for all-oxide solar cells with improved performance | |
| CN103219426A (en) | Extra small suede solar cell and preparation method thereof | |
| CN104269461B (en) | N-shaped In2s3the film build method of cushion and application thereof | |
| CN105244442A (en) | Thin film crystal silicon perovskite heterojunction solar cell manufacturing method | |
| CN104993004A (en) | Cuprous oxide based heterojunction solar cell and preparation method thereof | |
| CN102214737B (en) | Preparation method of compound thin film for solar battery | |
| CN104241439A (en) | Method for preparing cadmium telluride thin-film solar cell | |
| CN101882653B (en) | Preparation method of solar battery based on nano CdS (Cadmium Sulfide) film | |
| CN101820003A (en) | Doubles-layer zinc oxide transparent and conductive film for film solar cell and preparation method thereof | |
| CN110165020A (en) | One kind being based on CdS/SnO2Mix the efficient Sb of N-type layer2Se3Hull cell and preparation method thereof | |
| CN109037392A (en) | A kind of production technology of graphene/silicon structure solar battery | |
| CN102522505A (en) | Inorganic and organic hybrid solar cell | |
| CN101459206A (en) | Manufacturing process for high-efficiency multi-junction solar cell | |
| CN101707219B (en) | Solar cell with intrinsic isolation structure and production method thereof | |
| Kang et al. | Preparation and properties of CuInxGa1− xSe2 thin-film solar cell absorbers from selenization of Ga-rich electrodeposited precursors | |
| JP4550928B2 (en) | Photoelectric conversion element and solar cell using the same | |
| Musa et al. | Fabrication of p-Cu2O/n-Cu2O for photovoltaic applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201229 Address after: 245000 No.50, Meilin Avenue, Huangshan Economic Development Zone, Huangshan City, Anhui Province Patentee after: Huangshan Development Investment Group Co.,Ltd. Address before: Tunxi road in Baohe District of Hefei city of Anhui Province, No. 193 230009 Patentee before: Hefei University of Technology |